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   https://doi.org/10.1021/acs.jpca.8b05394  

   Weidman, Jared D.; Estep, Marissa L.; Schaefer, Henry F. (July 2018, The Journal of Physical Chemistry A)
2. Heterogeneous Electrocatalysts for Metal–CO ₂ Batteries and CO ₂ Electrolysis

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   Abstract Converting CO₂into industrially useful products is an appealing strategy for utilization of an abundant chemical resource. Electrochemical CO₂reduction (eCO₂R) offers a pathway to convert CO₂into CO and ethylene, using renewable electricity. These products can be efficiently copolymerized by organometallic catalysts to generate polyketones. However, the conditions for these reactions are very different, presenting the challenge of coupling microenvironments typically encountered for the transformation of CO₂into highly complex but desirable multicarbon products. Herein, we present a system to produce polyketone plastics entirely derived from CO₂and water, where both the CO and C₂H₄intermediates are produced by eCO₂R. In this system, a combination of Cu and Ag gas diffusion electrodes is used to generate a gas mixture with nearly equal concentrations of CO and C₂H₄, and a recirculatory CO₂reduction loop is used to reach concentrations of above 11% each, leading to a current‐to‐polymer efficiency of up to 51% and CO₂utilization of 14%. 

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4. Effect of “X” Ligands on the Photocatalytic Reduction of CO ₂ to CO with Re(pyridylNHC-CF ₃ )(CO) ₃ X Complexes: Effect of “X” Ligands on the Photocatalytic Reduction of CO ₂ to CO with Re(pyridylNHC-CF ₃ )(CO) ₃ X Complexes

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5. Reduction-induced CO dissociation by a [Mn(bpy)(CO) ₄ ][SbF ₆ ] complex and its relevance in electrocatalytic CO ₂ reduction

   https://doi.org/10.1039/c9dt04150h  

   Kuo, Hsin-Ya; Tignor, Steven E.; Lee, Tia S.; Ni, Danrui; Park, James Eujin; Scholes, Gregory D.; Bocarsly, Andrew B. (January 2020, Dalton Transactions)

   [Mn(bpy)(CO) 3 Br] is recognized as a benchmark electrocatalyst for CO 2 reduction to CO, with the doubly reduced [Mn(bpy)(CO) 3 ] − proposed to be the active species in the catalytic mechanism. The reaction of this intermediate with CO 2 and two protons is expected to produce the tetracarbonyl cation, [Mn(bpy)(CO) 4 ] + , thereby closing the catalytic cycle. However, this species has not been experimentally observed. In this study, [Mn(bpy)(CO) 4 ][SbF 6 ] ( 1 ) was directly synthesized and found to be an efficient electrocatalyst for the reduction of CO 2 to CO in the presence of H 2 O. Complex 1 was characterized using X-ray crystallography as well as IR and UV-Vis spectroscopy. The redox activity of 1 was determined using cyclic voltammetry and compared with that of benchmark manganese complexes, e.g. , [Mn(bpy)(CO) 3 Br] ( 2 ) and [Mn(bpy)(CO) 3 (MeCN)][PF 6 ] ( 3 ). Infrared spectroscopic analyses indicated that CO dissociation occurs after a single-electron reduction of complex 1 , producing a [Mn(bpy)(CO) 3 (MeCN)] + species. Complex 1 was experimentally verified as both a precatalyst and an on-cycle intermediate in homogeneous Mn-based electrocatalytic CO 2 reduction. 

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